US8592606B2 - Liquid precursor for depositing group 4 metal containing films - Google Patents
Liquid precursor for depositing group 4 metal containing films Download PDFInfo
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- US8592606B2 US8592606B2 US12/950,352 US95035210A US8592606B2 US 8592606 B2 US8592606 B2 US 8592606B2 US 95035210 A US95035210 A US 95035210A US 8592606 B2 US8592606 B2 US 8592606B2
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- C07F17/00—Metallocenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
Definitions
- This invention is in the field of volatile and liquid Group 4 metal complexes, as precursors for fabricating electronic devices by the semiconductor fabrication industries. Cyclopentadiene based Group 4, as well as other metal complexes, have been intensively explored as potential precursors.
- Prior art in this field includes:
- the present invention is related to a liquid titanium precursor represented by the formula:
- R 1 , R 2 and R 3 are the same or different and are selected from the group consisting of ethyl and isopropyl; and R 4 and R 4′ can be same or different and are selected from the group consisting of tert-butyl and tert-amyl, wherein when R 1 , R 2 and R 3 are isopropyl, R 4 is tert-amyl.
- the present invention is also related to Group 4 precursors represented by the formula:
- FIG. 1 provides the thermogravometric analysis (TGA) comparison for the evaporation of two Group 4 metal-containing precursors: (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium (represented by the solid line) and (2,5-di-tert-amylpyrrolyl)(tris(ethoxy)titanium (represented by the dashed line), demonstrating that both complexes have smooth and complete vaporization and suggesting that they can be used as potential volatile precursors for CVD or ALD
- FIG. 2 provides the thermograometric analysis (TGA) comparison of two Group 4 metal-containing precursors: (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium (represented by the solid line) and (2,5-di-tert-butylpyrrolyl)(tris(iso-propoxy)titanium (represented by the dashed line). Both show smooth one-step vaporizations. However the former is more volatile than the latter.
- TGA thermograometric analysis
- FIG. 3 provides the thermogravometric analysis (TGA) and differential scanning calorimetry (DSC) comparison of two Group 4 metal-containing precursors: (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium (represented by the solid line) and (2,5-di-methylpyrrolyl)(tris(ethoxy)titanium dimer (represented by the dashed line).
- TGA thermogravometric analysis
- DSC differential scanning calorimetry
- (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium is a liquid at room temperature and more volatile
- (2,5-di-methylpyrrolyl)(tris(ethoxy)titanium is a solid with melting point of 95° C., as shown in the DSC curve and less volatile, indicating that (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium is a superior precursor for CVD/ALD than (2,5-di-methylpyrrolyl)(tris(ethoxy)titanium dimer.
- FIG. 4 is a schematic representation of the crystal structure of (cyclopentadienyl)(2,5-di-methylpyrrolyl)(bis(ethoxy)titanium.
- FIG. 5 is the temperature dependence of the thermal ALD of titanium oxide film using 100 ALD cycles of ozone and (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium, indicating that ALD thermal window for this precursor is at least up to ⁇ 330° C.
- the present invention is related to a family of liquid Group 4 metal precursors represented by the formula: (pyr*)M(OR 1 )(OR 2 )(OR 3 ) wherein pyr* is an alkyl substituted pyrrolyl:
- Exemplary complexes include but not limited:
- R 4 and R 4′ are the same or different and are selected from the group consisting of tert-butyl and tert-amyl.
- R 4 is tert-amyl
- R 4′ is selected from the group consisting of tert-butyl and tert-amyl.
- Group 4 precursors is represented by the formula: (pyr*)(Cp)M(OR 1 )(OR 2 ), wherein pyr* is an alkyl substituted pyrrolyl and Cp is cyclopentadienyl or alkyl substituted cyclopentadienyl:
- a metal-containing film such as, but not limited to, strontium titanate and barium strontium titanate, titanium doped lanthanide oxide, titanium doped zirconium, titanium doped hafnium oxide using deposition processes, such as, but not limited to, atomic layer deposition (ALD) or cyclic chemical vapor deposition (CCVD) that may be used, for example, as a gate dielectric or capacitor dielectric film in a semiconductor device.
- ALD atomic layer deposition
- CCVD cyclic chemical vapor deposition
- MOS metal oxide semiconductor
- IC integrated circuit
- field effect semiconductor devices produce an output signal that is proportional to the width of the channel, such that scaling reduces their output.
- This effect has generally been compensated for by decreasing the thickness of gate dielectric, thus bring the gate in closer proximity to the channel and enhancing the field effect, which thereby increases the drive current. Therefore, it has become increasingly important to provide extremely thin reliable and low-defect gate dielectrics for improving device performance.
- the Group 4 precursor is thermally stable, and preferably in liquid form.
- Group 4-containing metal films are typically deposited using a vapor deposition (e.g., chemical vapor deposition and/or atomic layer deposition) process. It is desirable that these precursors are thermally stable during vapor delivery in order to avoid premature decomposition of the precursor, before it reaches the vapor deposition chamber during processing.
- Also described herein is a method for making a Group 4 metal-containing oxide film, metal-containing nitride film, metal-containing oxynitride film, metal-containing silicate film, multi-component metal oxide film, and any combination or laminate thereof, which may be used, for example, in fabricating semiconductor devices.
- the method disclosed herein provides a Group 4 metal or multi-component metal oxide film that has a dielectric constant substantially higher than that of either conventional thermal silicon oxide, silicon nitride, or zirconium/hafnium oxide dielectric.
- the method disclosed herein deposits the Group 4 metal containing films using atomic layer deposition (ALD) or chemical vapor deposition (CVD) processes, preferably an ALD process.
- ALD atomic layer deposition
- CVD chemical vapor deposition
- suitable deposition processes for the method disclosed herein include, but are not limited to, cyclic chemical vapor deposition (CCVD), MOCVD metal organic chemical vapor deposition (MOCVD), thermal chemical vapor deposition, plasma enhanced chemical vapor deposition (PECVD), photon assisted chemical vapor deposition (PACVD), plasma-photon assisted chemical vapor deposition (PPECVD), cryogenic chemical vapor deposition, chemical assisted vapor deposition, and hot-filament chemical vapor deposition.
- the metal containing films are deposited via thermal ALD or plasma enhanced cyclic ALD (PEALD) process.
- the deposition temperature may be relatively lower, preferably a range from 200° C. to 500° C., and may allow for a wider process window to control the specifications of film properties required in end-use applications.
- Exemplary deposition temperatures for the ALD or CCVD deposition include ranges having any one or more of the following endpoints: 200, 225, 250, 275, 300, 325, 350, 375, and/or 400° C.
- metal-containing precursors can be used in addition to the Group 4 metal-containing precursors described herein.
- Metals commonly used in semiconductor fabrication include those that can be used as the metal component such as: titanium, tantalum, tungsten, hafnium, zirconium, cerium, zinc, thorium, bismuth, lanthanum, strontium, barium, lead, and combinations thereof.
- Examples of other metal-containing precursors that may be used with the method disclosed herein include, but are not limited to, tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butylimino tri(diethylamino)tant
- a cyclic deposition process such as CCVD, ALD, or PEALD may be employed, wherein a Group 4 metal-containing precursor or its solution and an oxygen source such as, for example, ozone, oxygen plasma or water plasma are employed.
- the gas lines connecting from the precursor canisters to the reaction chamber are heated to one or more temperatures ranging from about 100° C. to about 200° C. depending upon the process requirements, and the container of the Group 4 metal-containing precursor is kept at one or more temperatures ranging from about 100° C. to about 190° C. for dispensing, wherein the solution comprising the Group 4 metal-containing precursor is injected into a vaporizer kept at one or more temperatures ranging from about 150° C. to about 200° C.
- a flow of 100-2000 sccm of inert gas such as argon or nitrogen may be employed as a carrier gas to help deliver the vapor of the Group 4 metal-containing precursor to the reaction chamber during the precursor pulsing.
- the reaction chamber process pressure is in the range of 0.1 to 10 Torr.
- the substrate such as silicon oxide or metal nitride
- the substrate are heated on a heater stage in a reaction chamber that is exposed to the Group 4 metal-containing precursor initially to allow the complex to chemically adsorb onto the surface of the substrate.
- An inert gas such as argon, purges away unadsorbed excess complex from the process chamber.
- an oxygen source is introduced into reaction chamber to react with the absorbed surface followed by another inert gas purge to remove reaction by-products from the chamber.
- the process cycle can be repeated to achieve the desired film thickness.
- the precursors described herein may be delivered in neat liquid form, or alternatively, may be dissolved in a suitable solvent or mixture of solvents and the resulting solution vaporized for us by DLI.
- the precursor formulations may include solvent component(s) of suitable character, as may be desirable and advantageous in a given end use application to form a film on a substrate.
- the solvent employed in solubilizing the precursor for use in a deposition process may comprise of any compatible solvent or mixtures of solvent, including; aliphatic hydrocarbons (e.g., pentane, hexane, heptane, octane, decane, dodecane, ethylcyclohexane, propylcyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, ethylbenzene, xylene, mesitylene, ethyl toluene and other alkyl substituted aromatic solvents), ethers, esters, nitriles, alcohols, amines (e.g., triethylamine, tert-butylamine), imines and carbodiimides (e.g., N,N′-diisopropylcarbodiimide), ketones, aldehydes, amidines, guanadines, is
- suitable solvents are selected from the group consisting of glyme solvents having from 1 to 6 oxygen atoms (e.g. dimethoxyethane, 1,2-diethoxyethane, diglyme and triglyme); organic ethers selected from the group consisting of propylene glycol groups (e.g. dipropylene glycol dimethyl ether); C 2 -C 12 alkanols; organic ethers selected from the group consisting of dialkyl ethers comprising C 1 -C 6 alkyl moieties, C 4 -C 8 cyclic ethers (e.g.
- a direct liquid delivery method can be employed by dissolving the Group 4 metal-containing precursor in a suitable solvent or a solvent mixture to prepare a solution with a molar concentration from 0.01 to 2 M, depending the solvent or mixed-solvents employed.
- the solvent employed herein may comprise any compatible solvents or their mixture including, but not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, linear or cyclic ethers, esters, nitriles, alcohols, amines, polyamines, aminoethers and organic amides, preferably a solvent with a high boiling point, such as octane, ethylcyclohexane, decane, dodecane, xylene, mesitylene and dipropylene glycol dimethyl ether.
- a solvent with a high boiling point such as octane, ethylcyclohexane, decane, dodecane, xylene, mesitylene and dipropylene glycol dimethyl ether.
- the resultant metal oxide films can be exposed to a post-deposition treatment, such as a thermal or plasma treatment to densify the film at temperature below 600° C.
- a post-deposition treatment such as a thermal or plasma treatment to densify the film at temperature below 600° C.
- the method described herein may be used to deposit a metal-containing film on at least a portion of a substrate.
- suitable substrates include, but are not limited to, semiconductor materials, such as strontium titanate, barium strontium titanate, yttrium oxide doped with titanium, lanthanum oxide doped with titanium, and other lanthanide oxides doped with titanium.
- FIG. 1 provides the thermogravometric analysis (TGA) comparison for the evaporation of two Group 4 metal-containing precursors: (2,5-di-tert-butyl)pyrrolyl)(tris(ethoxy)titanium (represented by the solid line) and (2,5-di-tert-amyl)pyrrolyl)(tris(ethoxy)titanium (represented by the dashed line).
- TGA thermogravometric analysis
- FIG. 2 provides the thermograometric analysis (TGA) curves and their corresponding first derivative (DTG) comparison of two Group 4 metal-containing precursors: (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium (represented by the solid line) and (2,5-di-tert-butylpyrrolyl)(tris(iso-propoxy)titanium (represented by the dashed line).
- X-ray diffraction of a crystal grown in hexane solution showed it is a dimer, in which two titanium atoms are bridged by two ethoxy groups. Each titanium is also coordinated to an additional two ethoxy groups and one 2,5-dimethylpyrrolyl via ⁇ 1 fashion.
- the structure is similar to (2,5-di-methylpyrrolyl)(tris(iso-propoxy)titanium dimer reported by Black, K., A. C. Jones, J. Bacsa, P. R. Chalker, P. A. Marshall, H. O. Davies, P. N. Heys, P. O'Brien, M. Afzaal, J. Raftery and G. W. Critchlow (2010).
- FIG. 3 provides TGA and DSC comparison of (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium (represented by the solid line) vs (2,5-di-methylpyrrolyl)(tris(ethoxy)titanium dimer (represented by the dashed line).
- (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium is a liquid at room temperature and more volatile
- (2,5-di-methylpyrrolyl)(tris(ethoxy)titanium dimer is a solid and less volatile, indicating (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium would be more desirable as a CVD/ALD precursor than (2,5-di-methylpyrrolyl)(tris(ethoxy)titanium dimer.
- FIG. 4 is the crystal structure, showing the cyclopentadienyl group coordinated in ⁇ 5 fashion to the titanium atom whereas the 2,5-dimethylpyrrolyl coordinated in ⁇ 1 coordination mode.
- This example describes an ALD of TiO 2 using (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium and ozone.
- the deposition temperature range is 200 ⁇ 400° C.
- the deposition chamber pressure is around 1.5 Torr.
- the container for (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium was kept at 100° C.
- One cycle of ALD or CCVD of TiO 2 consists of 4 steps.
- the typical ALD conditions are: Ti precursor pulse time was 4 or 8 seconds, the Ar purge time after Ti precursor pulse was 10 or 15 seconds, the ozone pulse time was 5 seconds, and the Ar purge time after ozone pulse was 10 seconds.
- the cycle was repeated 100 times. TiO 2 films were obtained and the dependence of titanium oxide thickness on deposition temperature is shown in FIG. 5 .
- the results suggest that ALD thermal process window can be up to ⁇ 330° C. with ALD growth rate of ⁇ 0.6 A/cycle which is much higher than what disclosed in prior art for solid precursors with similar ligand system (Black, K., A. C. Jones, J. Bacsa, P. R. Chalker, P. A. Marshall, H. O. Davies, P. N. Heys, P.
Abstract
Description
- Kuhn, N., et al., XVI. (2,5-C4t-Bu2RHN)MCl3 (M=Ti, Zr, Hf; R=H, SiMe3)—Azacyclopentadienyl-Komplexe der Gruppe 4-Metalle. Journal of Organometallic Chemistry, 440(3): p. 289-296, 1992.
- Dias, A. R., et al., Synthesis, characterisation, crystal structure, reactivity and bonding in titanium complexes containing 2,3,4,5-tetramethylpyrrolyl. Journal of the Chemical Society—Dalton Transactions, p. 1055-1061, 1996.
- Dussarrat, C., N. Blasco, A. Pinchart and C. Lachaud “Method of forming high-k dielectric films based on novel titanium, zirconium, and hafnium precursors and their use for semiconductor manufacturing.” WO2007140813.
- Dussarrat, C., N. Blasco, A. Pinchart and C. Lachaud “Method Of Forming Dielectric Films, New Precursors And Their Use In The Semi-Conductor Manufacturing.” WO2007141059A2 (US2009203222A).
- Heys, P. N., A. Kingsley, F. Song, P. Williams, T. Leese, H. O. Davies and R. Odedra “Methods Of Atomic Layer Deposition Using Titanium-Based Precursors.” US20090074983A1.
- Heys, P. N., A. Kingsley, F. Song, P. Williams, T. Leese, H. O. Davies and R. Odedra “Methods Of Preparing Thin Films By Atomic Layer Deposition Using Monocyclopentadienyl Trialkoxy Hafnium And Zirconium Precursors.” WO09036046.
- Heys, P. N., R. Odedra, A. Kingsley and H. O. Davies, “Titanium Pyrrolyl-Based Organometallic Precursors And Use Thereof For Preparing Dielectric Thin Films”, WO09155507 A1.
- Heys, P. N., R. Odedra, A. Kingsley and H. O. Davies, “Hafnium And Zirconium Pyrrolyl-Based Organometallic Precursors And Use Thereof For Preparing Dielectric Thin Films”, WO09155520 A1.
- Black, K., A. C. Jones, J. Bacsa, P. R. Chalker, P. A. Marshall, H. O. Davies, P. N. Heys, P. O'Brien, M. Afzaal, J. Raftery and G. W. Critchlow, “Investigation of new 2,5-dimethylpyrrolyl titanium alkylamide and alkoxide complexes as precursors for the liquid injection mocvd of TiO2.” Chemical Vapor Deposition 16(1-3): 93-99 (2010).
wherein R1, R2 and R3 are the same or different and are selected from the group consisting of ethyl and isopropyl; and R4 and R4′ can be same or different and are selected from the group consisting of tert-butyl and tert-amyl, wherein when R1, R2 and R3 are isopropyl, R4 is tert-amyl.
wherein M is a
wherein M is
- 1. (2,5-di-tert-butylpyrrolyl)(tris(methoxy)titanium
- 2. (2,5-di-tert-butylpyrrolyl)(tris(ethoxy)titanium
- 3. (2,5-di-tert-amylpyrrolyl)(tris(methoxy)titanium
- 4. (2,5-di-tert-amylpyrrolyl)(tris(ethoxy)titanium
- 5. (2,5-di-tert-amylpyrrolyl)(tris(iso-propoxy)titanium
- 6. (2,3,5-tri-tert-butylpyrrolyl)(tris(methoxy)titanium
- 7. (2,3,5-tri-tert-butylpyrrolyl)(tris(ethoxy)titanium
- 8. (2,3,5-tri-tert-butylpyrrolyl)(tris(iso-propoxy)titanium
- 9. (2,3,5-tri-tert-amylpyrrolyl)(tris(methoxy)titanium
- 10. (2,3,5-tri-tert-amylpyrrolyl)(tris(ethoxy)titanium
- 11. (2,3,5-tri-tert-amylpyrrolyl)(tris(iso-propoxy)titanium
- 12. (2,3,4,5-tetramethylpyrrolyl)(tris(methoxy)titanium
- 13. (2,3,4,5-tetramethylpyrrolyl)(tris(ethoxy)titanium
- 14. (2,3,4,5-tetramethylpyrrolyl)(tris(isoproxy)titanium
- 15. (2,5-di-tert-amylpyrrolyl)(tris(methoxy)zirconium
- 16. (2,5-di-tert-amylpyrrolyl)(tris(ethoxy)zirconium
- 17. (2,5-di-tert-amylpyrrolyl)(tris(iso-propoxy)zirconium
- 18. (2,3,5-tri-tert-amylpyrrolyl)(tris(methoxy)zirconium
- 19. (2,3,5-tri-tert-amylpyrrolyl)(tris(ethoxy)zirconium
- 20. (2,3,5-tri-tert-amylpyrrolyl)(tris(iso-propoxy)zirconium
- 21. (2,5-di-tert-amylpyrrolyl)(tris(methoxy)hafnium
- 22. (2,5-di-tert-amylpyrrolyl)(tris(iso-propoxy)hafnium
- 23. (2,5-di-tert-amylpyrrolyl)(tris(ethoxy)hafnium
- 24. (tetramethylpyrrolyl)(tris(ethoxy)hafnium
- 25. (2,3,4,5-tetramethylpyrrolyl)(tris(isoproxy)hafnium
wherein R4 and R4′ are the same or different and are selected from the group consisting of tert-butyl and tert-amyl.
wherein M is
- 1. (cyclopentadienyl)(2-methylpyrrolyl)(bis(ethoxy)titanium
- 2. (methylcyclopentadienyl)(2-methylpyrrolyl)(bis(ethoxy)titanium
- 3. (ethylcyclopentadienyl)(2-methylpyrrolyl)(bis(ethoxy)titanium
- 4. (propylcyclopentadienyl)(2-methylpyrrolyl)(bis(ethoxy)titanium
- 5. (cyclopentadienyl)(2-methylpyrrolyl)(bis(methoxy)titanium
- 6. (methylcyclopentadienyl)(2-methylpyrrolyl)(bis(methoxy)titanium
- 7. (ethylcyclopentadienyl)(2-methylpyrrolyl)(bis(methoxy)titanium
- 8. (propylcyclopentadienyl)(2-methylpyrrolyl)(bis(methoxy)titanium
- 9. (cyclopentadienyl)(2,5-di-methylpyrrolyl)(bis(ethoxy)titanium
- 10. (cyclopentadienyl)(2,5-di-methylpyrrolyl)(bis(methoxy)titanium
- 11. (methylcyclopentadienyl)(2,5-di-methylpyrrolyl)(bis(methoxy)titanium
- 12. (ethylcyclopentadienyl)(2,5-di-methylpyrrolyl)(bis(methoxy)titanium
- 13. (propylcyclopentadienyl)(2,5-di-methylpyrrolyl)(bis(methoxy)titanium
- 14. (methylcyclopentadienyl)(2,5-di-methylpyrrolyl)(bis(ethoxy)titanium
- 15. (ethylcyclopentadienyl)(2,5-di-methylpyrrolyl)(bis(ethoxy)titanium
- 16. (propylcyclopentadienyl)(2,5-di-methylpyrrolyl)(bis(ethoxy)titanium
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JP2012193445A (en) * | 2011-02-28 | 2012-10-11 | Tokyo Electron Ltd | Method of forming titanium nitride film, apparatus for forming titanium nitride film, and program |
TW201402586A (en) * | 2012-05-25 | 2014-01-16 | Air Liquide | Hafnium-containing precursors for vapor deposition |
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